CN1037721A - 热固性树脂组合物 - Google Patents
热固性树脂组合物 Download PDFInfo
- Publication number
- CN1037721A CN1037721A CN89103316A CN89103316A CN1037721A CN 1037721 A CN1037721 A CN 1037721A CN 89103316 A CN89103316 A CN 89103316A CN 89103316 A CN89103316 A CN 89103316A CN 1037721 A CN1037721 A CN 1037721A
- Authority
- CN
- China
- Prior art keywords
- compositions
- thermosetting resin
- logical formula
- resin
- aromatic amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 83
- 239000011347 resin Substances 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 35
- -1 bismaleimide compound Chemical class 0.000 claims abstract description 42
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 30
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 238000009998 heat setting Methods 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- ZUVPLKVDZNDZCM-UHFFFAOYSA-N 3-chloro-2-methylaniline Chemical compound CC1=C(N)C=CC=C1Cl ZUVPLKVDZNDZCM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical group CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- FRCFWPVMFJMNDP-UHFFFAOYSA-N n-propan-2-ylaniline Chemical group CC(C)NC1=CC=CC=C1 FRCFWPVMFJMNDP-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VKTQADPEPIVMHK-UHFFFAOYSA-N (2-phenylphenyl)methanol Chemical group OCC1=CC=CC=C1C1=CC=CC=C1 VKTQADPEPIVMHK-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UVXKCEMBYZHXMM-UHFFFAOYSA-N 1,1-dimethyl-2,3-dihydroindene-4,6-diamine Chemical compound C1=C(N)C=C(N)C2=C1C(C)(C)CC2 UVXKCEMBYZHXMM-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NLWCWEGVNJVLAX-UHFFFAOYSA-N 1-methoxy-2-phenylbenzene Chemical compound COC1=CC=CC=C1C1=CC=CC=C1 NLWCWEGVNJVLAX-UHFFFAOYSA-N 0.000 description 1
- OEWYVHJLQDINFS-UHFFFAOYSA-N 2-(2-aminoethyl)aniline Chemical compound NCCC1=CC=CC=C1N OEWYVHJLQDINFS-UHFFFAOYSA-N 0.000 description 1
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical class CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 description 1
- JEPCLNGRAIMPQV-UHFFFAOYSA-N 2-aminobenzene-1,3-diol Chemical compound NC1=C(O)C=CC=C1O JEPCLNGRAIMPQV-UHFFFAOYSA-N 0.000 description 1
- WYWNLVJBQRJIOU-UHFFFAOYSA-N 2-methyl-4-propan-2-ylaniline Chemical compound CC(C)C1=CC=C(N)C(C)=C1 WYWNLVJBQRJIOU-UHFFFAOYSA-N 0.000 description 1
- PZOZYLSYQJYXBI-UHFFFAOYSA-N 2-propan-2-yloxyaniline Chemical compound CC(C)OC1=CC=CC=C1N PZOZYLSYQJYXBI-UHFFFAOYSA-N 0.000 description 1
- KWTZFUAWBOIKBN-UHFFFAOYSA-N 2-tert-butylbenzene-1,3-diamine Chemical compound CC(C)(C)C1=C(N)C=CC=C1N KWTZFUAWBOIKBN-UHFFFAOYSA-N 0.000 description 1
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- GDJLLPTUSIUMOM-UHFFFAOYSA-N 3-ethyl-2-methylaniline Chemical compound CCC1=CC=CC(N)=C1C GDJLLPTUSIUMOM-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OMVFXCQLSCPJNR-UHFFFAOYSA-N 4-amino-2,6-dimethylphenol Chemical compound CC1=CC(N)=CC(C)=C1O OMVFXCQLSCPJNR-UHFFFAOYSA-N 0.000 description 1
- ZYZQSCWSPFLAFM-UHFFFAOYSA-N 4-amino-2-chlorophenol Chemical class NC1=CC=C(O)C(Cl)=C1 ZYZQSCWSPFLAFM-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- JCLZLZKUISPXDC-UHFFFAOYSA-N 4-chloro-2,6-dimethylaniline Chemical compound CC1=CC(Cl)=CC(C)=C1N JCLZLZKUISPXDC-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- PTMVFRKAMOUORT-UHFFFAOYSA-N 4-ethylbenzene-1,3-diamine Chemical compound CCC1=CC=C(N)C=C1N PTMVFRKAMOUORT-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- IPDXWXPSCKSIII-UHFFFAOYSA-N 4-propan-2-ylbenzene-1,3-diamine Chemical compound CC(C)C1=CC=C(N)C=C1N IPDXWXPSCKSIII-UHFFFAOYSA-N 0.000 description 1
- JFQJDZQPICZGJF-UHFFFAOYSA-N 4-tert-butylbenzene-1,3-diamine Chemical compound CC(C)(C)C1=CC=C(N)C=C1N JFQJDZQPICZGJF-UHFFFAOYSA-N 0.000 description 1
- QHWIAGPQYKXGQV-UHFFFAOYSA-N 5-methyl-3-(2-methylpropyl)hexan-2-one Chemical compound CC(C)CC(C(C)=O)CC(C)C QHWIAGPQYKXGQV-UHFFFAOYSA-N 0.000 description 1
- WEBFIEBRATXTAO-UHFFFAOYSA-N 5-tert-butyl-2-ethylaniline Chemical compound CCC1=CC=C(C(C)(C)C)C=C1N WEBFIEBRATXTAO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- SSFGHKDDKYEERH-UHFFFAOYSA-N [6-(hydroxymethyl)naphthalen-2-yl]methanol Chemical compound C1=C(CO)C=CC2=CC(CO)=CC=C21 SSFGHKDDKYEERH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229960005081 diclofenamide Drugs 0.000 description 1
- QTURWMMVIIBRRP-UHFFFAOYSA-N diethoxymethoxybenzene Chemical compound CCOC(OCC)OC1=CC=CC=C1 QTURWMMVIIBRRP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 1
- BHTUNQYYFYCLDV-UHFFFAOYSA-N phenoxymethanediol Chemical compound OC(O)OC1=CC=CC=C1 BHTUNQYYFYCLDV-UHFFFAOYSA-N 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
- C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/123—Unsaturated polyimide precursors the unsaturated precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本文公开了一种热固性树脂组合物,它包括100重量份通式(I)表示的双马来酰亚胺化合物和5~100重量份通式(II)表示的芳族胺树脂,
式中R和A如权利要求1所定义。由本发明的组合物经热固化而得到的模塑制品有优异的机械强度和耐热性。
Description
本发明涉及一种用来制造保持耐热性而又具有好的机械强度的模塑制品的新型热固性树脂组合物。
迄今为止,具有酰亚胺结构的每种热固性树脂都广泛地用于各个工业领域,因为由这些热固性树脂得到的固化材料具有较好的电绝缘性、耐热性及尺寸稳定性。
然而,只由芳族双马来酰亚胺经热聚合而得到的热固性树脂是极脆的,而且有柔韧性很差的缺点,尽管其耐热性极好。为了消除这个障碍,已对许多热固性树脂组合物进行了尝试,它们每一种都含有芳族双马来酰亚胺和芳族二胺。例如,含有N,N′-4,4′-二苯基甲烷双马来酰亚胺和4,4′-二胺基二苯基甲烷的聚胺基双马来酰亚胺树脂(Rhone-Poulenc公司制商品名Kelimid),现在已经实施并广泛用于层压塑料浸渍液、层压板及模塑制品等(日本专利公告号23250/1971)。
不过,上述的热固性树脂组合物,其耐热性差,抗冲击和柔韧性也不令人满意。
本发明的一个目的是提供一种热固性树脂组合物,可用于制造具有良好机械强度和耐热性的模塑制品。
借如下热固性树脂组合物就能实现上述目标,这种组合物含有100重量份如通式(Ⅰ)所示的双马来酰亚胺化合物和5~100重量份如通式(Ⅱ)所示的芳族胺树脂:
式中A是亚苯基、烷基取代的亚苯基、二亚苯基、二苯醚基或亚萘基;R1是卤原子、羟基、有4个或少于4个碳原子的烷氧基或有5个或少于5个碳原子的烷基;l是1或2;m是0至3的整数;当m为2或3时,R1表示的基团可以相同也可不同,或者其中的两个基团构成具有侧链的五元或六元脂族环;n是0~300的整数。
通式(Ⅰ)所表示的双马来酰亚胺化合物可以由马来酸酐和通式(Ⅲ)所表示的二胺化合物通过按通常的方法缩合/脱水反应而制备:
这里R是二价 基,其中,X直接连在苯环上,可由以下一组基团中选用:具有1~10个碳原子的二价烃基、具有6个氟原子的异亚丙基、羰基、硫基、亚磺酰基、磺酰基和氧基。
在双马来酰亚胺化合物(Ⅰ)中,链节R的实例包括:
本发明使用的双马来酰亚胺化合物(Ⅰ)的典型实例包括:1,3-双(3-马来酰亚胺基苯氧基)苯、双〔4-(3-马来酰亚胺基苯氧基)苯基〕甲烷、1,1-双〔4-(3-马来酰亚胺基苯氧基)苯基〕乙烷、1,2-双〔4-(3-马来酰亚胺基苯氧基)苯基〕乙烷、2,2-双〔4-(3-马来酰亚胺基苯氧基)苯基〕丙烷、2,2-双〔4-(3-马来酰亚胺基苯氧基)苯基〕丁烷、2,2-双〔4-(3-马来酰亚胺基苯氧基)苯基〕-1,1,1,3,3,3-六氟丙烷、4,4′-双(3-马来酰亚胺基苯氧基)联苯、双〔4-(3-马来酰亚胺基苯氧基)苯基〕酮、双〔4-(3-马来酰亚胺基苯氧基)苯基〕硫醚、双〔4-(3-马来酰亚胺基苯氧基)苯基〕亚砜、双〔4-(3-马来酰亚胺基苯氧基)苯基〕砜和双〔4-(3-马来酰亚胺基苯氧基)苯基〕醚。它们可单独使用或混合使用。
本发明中使用的特定芳族胺树脂(Ⅱ)可通过1摩尔通式(Ⅳ)表示的芳烷基醇衍生物和1~15摩尔通式(Ⅴ)表示的芳族胺化合物进行反应而制备:
其中A为亚苯基、烷基取代的亚苯基、二亚苯基、二苯醚或亚萘基,R2是氢原子或酰基或有4个或少于4个碳原子的烷基,
其中R1是卤原子、羟基、具有4个或少于4个碳原子的烷氧基或具有5个或少于5个碳原子的烷基;l是1或2;m是0至3的整数,且当m为2或3时,R1所表示的基团可相同或不同,或者其中两个基团能构成可具有侧链的五元或六元脂族环(日本专利申请号252517/1987)。
式(Ⅳ)中的R2是氢原子、酰基或烷基。这些基团的典型实例包括α,α′-二羟基-邻二甲苯、α,α′-二羟基-间二甲苯、α,α′-二羟基-对二甲苯、α,α′-二乙酰氧基-邻二甲苯、α,α′-二乙酰氧基-间二甲苯、α,α′-二乙酰氧基-对二甲苯、α,α′-二丙氧基-对二甲苯,α,α′-二正丁氧基-对二甲苯、α,α′-二甲氧基-邻二甲苯、α,α′-二甲氧基-间二甲苯、α,α′-二甲氧基-对二甲苯、α,α′-二乙氧基-邻二甲苯、α,α′-二乙氧基-间二甲苯、α,α′-二乙氧基-对二甲苯、α,α′-二异丙氧基-邻二甲苯、α,α′-二异丙氧基-间二甲苯、α,α′-二异丙氧基对二甲苯、α,α′-二正丙氧基-对二甲苯、α,α′-二正丁氧基-间二甲苯、α,α′-二正丁氧基-对二甲苯,α,α′-二仲丁氧基-对二甲苯、α,α′-二异丁氧基-对二甲苯、4,4′-二羟甲基二苯醚、4,4′-二羟甲基联苯、2,6-二羟甲基萘、4,4′-二乙酰氧基甲基二苯醚、4,4′-二乙酰氧甲基联苯、2,6-二乙酰氧甲基萘、4,4′-甲氧基二苯醚、4,4′-甲氧甲基联苯、4,4′-二乙氧甲基苯基醚、4,4′-二异丙氧甲基联苯、4,4′-二异丁氧甲基二苯醚、α,α′-二甲氧基-2-甲基-对二甲苯、α,α′-二甲氧基-3-甲基-间二甲苯、α,α′-二羟基-2,5-二甲基-对二甲苯、α,α′-二甲氧基-2,5-二甲基-对二甲苯、α,α′-二甲氧基-2,4-二甲基-1,3-二甲苯和α,α′-二甲氧基-2,4-二甲基-1,5-二甲苯。在上述所有化合物中以α,α′-二甲氧基-对二甲苯为最好。
通式(Ⅴ)所代表的芳族胺化合物中,R1是卤原子、羟基、具有4个或少于4个碳原子的烷氧基或具有5个或少于5个碳原子的烷基。R1所表示的基团数为0至3,当此基团数为2或3时,R1所表示的基团可以相同或不同,或者其中两个基团能构成可具有侧链的脂族五元或六元环。
较好的R1是具有1~3个碳原子的烷基、羟基或卤原子,在通式(Ⅴ)中R1不存在也是较好的。岩棉、陶瓷纤维、氧化铝纤维或钛酸钾纤维,或有机纤维如碳纤维或聚芳酰胺。
(c)、用于改进在最终涂膜、粘合层或树脂模塑制品中使用树脂性能的各种合成树脂:例如,热固性树脂如酚醛树脂、环氧树脂或三聚氰胺树脂,或聚硅氧烷树脂、聚酰胺、聚碳酸酯、聚砜、聚醚砜、聚醚醚酮、改性聚苯醚、聚苯硫醚、聚醚酰亚胺和含氟树脂。
本发明的热固性树脂组合物能够用已知的模塑技术进行模塑,例如压塑、传递模塑、挤塑或注塑,此组合物也有优异的可模塑性。
此外,由本发明的热固性树脂组合物制得的模塑制品具有优异的机械强度和耐热性,此组合物可望用于电气及电子领域,以及飞行器及车辆的机械领域。因此,公正地说,本发明的热固性树脂组合物具有很大的工业应用的意义。
现在,参照实例来详细地叙述本发明。
合成实例1
在装有搅拌器、温度计和Dean Stark共沸蒸馏阱的反应釜中,装入如通式(Ⅴ)所表示芳族胺化合物的1,116克(12.0摩尔)苯胺,如通式(Ⅳ)所表示芳烷基醇类衍生物的665克(4.0摩尔)α,α′-二甲氧基对二甲苯,以及作为催化剂的35%626克(6.0摩尔)盐酸的水溶液,在通入氮气下将溶液升温。当反应容器中的温度即内温达到110℃左右时,水开始蒸出,并在阱中收集,收集到的水从系统中排出。此后,进一步升温,当温度达到130℃左右时,可见到蒸出甲醇。在蒸出甲醇时,温度进一步升高,内温达到170℃,并在此温度下维持3小时。经过这段时间以后,确认甲醇产生已很少。然后,不断地升高内温,在190~200℃下进行反应12小时。代表的碱中和,然后用水洗涤。然后,在减压下从系统中除去未反应的芳族胺化合物,这样就得到了具有通式(Ⅱ)的所需芳族胺树脂。
得到的芳族胺树脂的分子量为约300~约60,000,其软化点在常温范围,在常温下至约250℃它是液体(按JIS-K-2548标准环球法测定)。
芳族胺树脂的分子量最好为300~20,000,而软化点为常温,在常温至200℃时,它是液体。
芳族胺树脂(Ⅱ)的实例为
可以由式(1)所表示的双马来酰亚胺类化合物和式(Ⅱ)所表示的芳族胺树脂制备本发明的热固性树脂组合物,在此情况下,可使用下述几种方法中的任何一种。
(1)以固-固态或固-液态将双马来酰亚胺和芳族胺树脂研碎并混合。或者是将这些物质进行热处理,以形成预聚物,然后再研成颗粒或粉末。在此情况下,最好使得加热的条件让固化过程部分地达到预聚物的阶段,热处理一般在70~220℃进行5~240分钟,最好在80~200℃的温度下进行10~180分钟。
(2)将双马来酰亚胺和芳族胺树脂溶于有机溶剂,然后将溶液加到劣溶剂中,以使结晶沉淀,然后过滤收集结晶,干燥得到粒状物或粉末。也可以在溶于有机溶剂后,将物料进行热处理,以使其部分固化直至预聚物阶段,然后再加入到劣溶剂中。再经过滤收集沉淀出的结晶并干燥以得到颗粒或粉末。在此情况下,加热条件与上述第(1)方法相同。
所用的有机溶剂必须满足要求,即它不与这两种组分中的任一种发生反应,此外,还希望有机溶剂对这两个组分都是良溶剂。通常可以使用的反应溶剂的实例包括卤代烃,如二氯甲烷、二氯乙烷和三氯乙烷;酮类如丙酮、甲乙酮、环己酮和二异丙酮;醚类如四氢呋喃、二氧六环和甲基溶纤剂;芳族化合物如苯、甲苯和氯苯;以及非质子极性溶剂如乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮和1,3-二甲基咪唑烷酮。
由式(Ⅱ)表示的芳族胺树脂用量以式(Ⅰ)表示的双马来酰亚胺为100重量份为基础,则在5~100重量份,最好为5~80重量份。
当芳族胺树脂的用量少于5重量份时,由其制备的固化制品十分脆,因此得不到令人满意的弯曲强度。相反,若多于100重量份,则固化制品的耐热性低。
在本发明的热固性树脂组合物中,可加入如下的a、b和c组份,其加入量只要不妨碍本发明目的即可。
(a)、固化促进剂:例如,象偶氮或有机过氧化物之类的游离基聚合引发剂,或如叔胺、季铵盐、咪唑或三氟化硼/胺盐的离子型催化剂。
(b)、粉末增强材料或填料:例如,象氧化铝或氧化镁的金属氧化物、如氢氧化铝的金属氢氧化物、如碳酸镁的金属碳酸盐、硅藻土粉、碱式硅酸镁、烧结粘土、细二氧化硅粉末、熔融二氧化硅、石英粉、碳黑、高岭土、细云母粉、石英粉、石墨、石棉、二硫化钼或三氧化锑。还有,纤维状增强材料或填料:例如,无机纤维如玻璃纤维、
在通式(Ⅴ)所表示的胺类化合物中胺基数是1或2,最好是1。胺基化合物的典型实例包括苯胺、邻甲苯胺、间甲苯胺、对甲苯胺、邻乙苯胺、间乙苯胺、对乙苯胺、邻异丙苯胺、间异丙苯胺、对异丙苯胺、邻正丙苯胺、邻叔丁苯胺、对叔丁苯胺、邻正丁苯胺、对仲丁苯胺、2,3-二甲代苯胺、2,4-二甲代苯胺、2,6-二甲代苯胺、3,4-二甲代苯胺、3,5-二甲代苯胺、2-甲基-3-乙基苯胺、2-甲基-4-异丙基苯胺、2,6-二乙基苯胺、2-乙基-5-叔丁基苯胺、2,4-二异丙基苯胺、2,4,6-三甲基苯胺、4-氯苯胺、4-溴苯胺、4-氟苯胺、3-氯苯胺、3-溴苯胺、3,4-二氯苯胺、3-氯邻甲苯胺、3-氯对甲苯胺、2,6-二甲基-4-氯苯胺、邻氨基苯酚、间氨基苯酚、对氨基苯酚、2-氨基-4-甲酚、4-氨基-2-叔丁基苯酚、2,6-二甲基-4-氨基苯酚、2,6-二氯-4-氨基苯酚、2-氨基-1,3-间苯二酚、4-氨基-1,3-间苯二酚、2-氨基对苯二酚、2-甲氧基苯胺、3-甲氧基苯胺、4-甲氧基苯胺、2-异丙氧基苯胺、2,4-二甲氧基苯胺、邻苯二胺、间苯二胺、对苯二胺、2,4-二氨基甲苯、2,6-二氨基甲苯、2,4-二氨基乙苯、2,6-二氨基乙苯、2,4-二氨基异丙苯、2,4-二氨基叔丁苯、2,6-二氨基叔丁苯、2,4-二氨基-1,3-二甲基苯、1,1-二甲基-4-氨基茚满和1,1-二甲基-4,6-二氨基茚满。在以上所有胺类中,苯胺、甲苯胺、二甲苯胺、氨基苯酚和二胺类是较好的,而苯胺特别好。
关于芳烷基醇类衍生物(Ⅳ)和芳族胺类化合物的反应,缩合反应是在芳族胺化合物与芳烷基醇类衍生物的摩尔比为1~15、最好为1.1~10的条件下,在170~240℃的温度下、在酸性催化剂如氢氯酸存在下、进行10~40小时完成。在反应完成后,用以苛性钠为
在这以后,用冷却的方法将内温降至95℃,然后加入1,680克15%的苛性钠溶液,继之以搅拌和中和。搅拌停止后,产生的下层水层从容器中排出,然后加入3,000克饱和盐溶液,然后洗涤和分离。下一步,在氮气流下进行加热和脱水,然后压滤以从中除去无机盐等。此后,在2~3毫米汞柱的低压下浓缩溶液,回收519克未反应的苯胺。收集剩下的溶液,从中得到945克浅黄棕色的苯胺树脂(芳族胺树脂)。
然后用高速液相色谱法分析如此得到的芳族胺树脂。结果,可明显地看到,作为通式(Ⅱ)的化合物,n=0的化合物占28%(摩尔),n=1的化合物占16.8%(摩尔),n=2的化合物占10.5%,n=3的化合物占7.8%而n≥4的化合物占36.9%(摩尔)。
进一步看如此得到的树脂,其胺当量为0.578当量/100克(高氯酸-冰醋酸法);根据JIS-K-2548的环球法软化点测定法测得的软化点为68℃。此外,树脂的平均分子量为960。
合成实例2
按照与合成实例1中相同的方法,不同之处是使用745克(80摩尔)苯胺、664克(4.0摩尔)α,α′-二甲氧基对二甲苯和420克(4.0摩尔)用作催化剂的35%盐酸水溶液进行反应,得到747克浅黄棕色的苯胺树脂(芳族胺树脂)。
然后,用高速液相色谱分析如此得到的芳族胺树脂。结果,明显地看到,通式(Ⅱ)所表示的化合物,其中n=0的化合物占17.0%(摩尔)、n=1的化合物占14.5%(摩尔)、n=2的化合物占13.2%(摩尔)、而n≥3的化合物占55.2%(摩尔)。
另外,得到的树脂,其胺当量为0.520当量/100克,其软化点为61℃,其平均分子量为2,100。
合成实例3
按照与合成实例1所述相同的方法,不同之处是使用244.4克(2.0摩尔)2,4-二氨基甲苯作为通式(Ⅴ)表示的芳族胺化合物和209克(2.0摩尔)的35%盐酸水溶液作为催化剂进行反应,得到132克红棕色油状二氨基甲苯树脂(芳族胺树脂)。
然后用高速液相色谱分析如此得到的芳族胺树脂。结果,可明显地看到,作为通式(Ⅱ)表示的化合物,其中n=0的化合物占44.5%(摩尔)、n=1的化合物占29.7%(摩尔)、n=2的化合物占14.6%(摩尔)而n≥3的化合物为11.2%(摩尔)。
另外对于得到的树脂,其胺当量为1.204,其软化点为46℃,平均分子量为550。
合成实例4
按照与合成实例1所述相同的方法,不同之处是使用121.1克(1.3摩尔)苯胺作为通式(Ⅴ)所表示的芳族胺树脂、138.2克(1.0摩尔)α,α′-二羟基间二甲苯作为通式(Ⅳ)所表示的芳烷基醇类衍生物和33克(0.325摩尔)的浓硫酸作为催化剂进行反应,得到151克浅黄棕色的苯胺树脂(芳族胺树脂)。
另外对于得到的芳族胺树脂,其胺当量为0.496,用按照JIS-K-2548规定的环球法软化点测定法测量其软化点为118℃,其平均分子量为6,500。
合成实例5
在一反应釜中加入109克(1.0摩尔)对氨基苯酚作为通式(Ⅴ)所表示的芳族胺化合物、110.2克(0.5摩尔)α,α′-二乙酰氧基对二甲苯作为通式(Ⅳ)所表示的芳烷基醇类衍生物和6.8克(0.05摩尔)氯化锌和19克(0.1摩尔)对甲基苯磺酸作为催化剂,反应在水喷射泵形成的负压下进行。反应在约30℃开始,在3小时的时间温度升至170℃。其间,通过深冷阱回收生成的乙酸。保持此温度3小时,然后反应温度升至200℃。然后在200~210℃的温度下老化1小时,在这时,反应进行到底了。在这之后,将溶液冷却至95℃,加入300毫升甲苯,接着搅拌和溶解。此后,加入20.2克三乙胺,再加入200毫升水。将溶液搅拌再静置,除去在下部形成的水层。再用200毫升的水洗涤再洗一次,并除去水层。此后,在减压下浓缩溶液以从中除去甲苯和未反应的对氨基苯酚,这样得到138克棕色残留物,即对氨基苯酚的共缩合树脂(芳族胺树脂)。
对于如此得到的芳族胺树脂,其胺当量为0.525,按JIS-K-2548中规定的环球法软化点测量法测得的软化点为94℃,其平均分子量为2,200。
合成实例6~14
用与合成实例1所述相同的方法进行反应,不同之处在于使用的通式(Ⅴ)所表示的芳族胺化合物、通式(Ⅴ)所表示的芳烷基醇类衍生物的种类和用量、催化剂的种类和用量以及反应条件,这都如表1所示,由此得到如表1所示的各种芳族胺树脂。
实例1至4
在一个装有搅拌器、迴流冷凝器和氮气导入管的不锈钢反应釜中加入4,4′-双(3-马来酰亚胺基苯氧基)联苯和合成实例1得到的芳族胺树脂,用量如表2所示,将其在180℃加热熔融20分钟。此后,在150℃和减压(10~15毫米汞柱)下进行脱泡30分钟,然后将物料冷至室温,得到固化后呈玻璃态的棕色半透明树脂组合物。
将一个模具加热至180℃,然后用如此得到的组合物充入模具,当组合物加热熔融时,将其在50千克/厘米2压力下维持30分钟以进行压塑。在此之后,从中取出模塑制品。在烘箱中250℃让制品进一步进行4小时后固化,这样制得127毫米长、12.7毫米长、6.4毫米厚的固化试样。
对于用上述方法制备的各个试样,按照ASTM-D-648和ASTM-D-790的方法测定热变形温度和弯曲强度,也测量了升温速度为10℃/分时在空气中开始热分解的温度。结果列在表2。
实例5~20和对比例1和2
重复与实例1~4所述相同的方法,不同之处是使用100重量份表2所示的各种双马来酰亚胺化合物和表2所示数量的各种芳族胺树脂。结果也列在表2中。
对比例3
重复与实例1~4所述相同的方法,不同之处是使用表2中所示数量的N,N′-4,4′-二苯基甲烷双马来酰亚胺和4,4′-二氨基二苯基甲烷。结果列在表2。
对比例4
按照与实例1~4所述相同的方法制备模塑试样,不同之处是用聚氨基双马来酰亚胺树脂(日本聚酰亚胺公司制造,商品名Kelimid-1050)代替本发明的树脂组合物,并测量各种物理性能。结果列在表2中。
按照表2中的结果,由本发明的热固性树脂组合物得到的模塑制品具有高弯曲强度和弯曲弹性模量,热变形温度为290℃或更高,开始热分解的温度为350℃或更高,这表明,本发明组合物得到的制品耐热性也是很优异的。
Claims (18)
2、按照权利要求1的热固性树脂组合物,其特征在于在通式(Ⅰ)中的所述R是一个具有如下结构的二价基团:
7、按照权利要求1的热固性树脂组合物,其特征在于通式(Ⅱ)中的所述R1是含有1~3个碳原子的烷基、羟基或卤原子。
8、按照权利要求1的热固性树脂组合物,其特征在于通过(Ⅱ)中的所述m为0。
9、按照权利要求1的热固性树脂组合物,其特征在于通式(Ⅱ)中的所述l是1。
10、按照权利要求1的热固性树脂组合物,其特征在于通式(Ⅱ)的芳族胺树脂是:
12、按照权利要求10的热固性树脂组合物,其特征在于通式(Ⅰ)的双马来酰亚胺化合物是:
15、按照权利要求1的热固性树脂组合物,其特征在于此组合物是将100重量份通式(Ⅰ)的双马来酰亚胺化合物同5~80重量份通式(Ⅱ)的芳族胺树脂混合而制备。
16、按照权利要求1的热固性树脂组合物,其特征在于此组合物是在70~220℃的温度下,将通式(Ⅰ)的双马来酰亚胺化合物和通式(Ⅱ)的芳族胺树脂的混合物加热10~180分钟,使所述混合物部分固化达到预聚物阶段而制备。
17、按照权利要求1的热固性树脂组合物,其特征在于所述芳族胺树脂的分子量为300~60,000。
18、按照权利要求1的热固性树脂组合物,其特征在于所述芳族胺树脂的分子量为300~20,000。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63118363A JPH075737B2 (ja) | 1988-05-17 | 1988-05-17 | 熱硬化性樹脂組成物 |
JP118363/88 | 1988-09-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1037721A true CN1037721A (zh) | 1989-12-06 |
Family
ID=14734850
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN89103316A Pending CN1037721A (zh) | 1988-05-17 | 1989-05-17 | 热固性树脂组合物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US4959443A (zh) |
EP (1) | EP0342943B1 (zh) |
JP (1) | JPH075737B2 (zh) |
KR (1) | KR930002238B1 (zh) |
CN (1) | CN1037721A (zh) |
AU (1) | AU611801B2 (zh) |
CA (1) | CA1333947C (zh) |
DE (1) | DE68908009T2 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1317329C (zh) * | 2003-11-05 | 2007-05-23 | 三井化学株式会社 | 树脂组合物、使用该树脂组合物的预浸料及叠层板 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5244999A (en) * | 1988-02-26 | 1993-09-14 | Petrochemie Danubia Gesellschaft M.B.H. | Polyimide from diamine and bismaleimide having azole ring |
AT390059B (de) * | 1988-02-26 | 1990-03-12 | Danutec Werkstoff | Diamine und bismaleinimide, sowie daraus hergestellte polyimide |
US5082880A (en) * | 1988-09-12 | 1992-01-21 | Mitsui Toatsu Chemicals, Inc. | Semiconductor sealing composition containing epoxy resin and polymaleimide |
AU626940B2 (en) * | 1988-10-28 | 1992-08-13 | Advanced Elastomer Systems, L.P. | Dynamically vulcanized alloys of crystalline polyolefin resin and halobutyl rubber material |
FR2645539B1 (fr) * | 1989-04-10 | 1991-06-14 | Rhone Poulenc Chimie | Polymeres a groupements imides faits a partir de diamines encombrees |
FR2645540B1 (fr) * | 1989-04-10 | 1991-06-14 | Rhone Poulenc Chimie | Polymeres a groupements imide a base de maleimides dont un bismaleimide siloxane et de diamines aromatiques et leur procede de preparation |
US5106937A (en) * | 1990-04-11 | 1992-04-21 | Mitsui Toatsu Chemicals, Inc. | Thermosetting resin from penta arylene bis maleimide |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH620938A5 (zh) * | 1976-04-08 | 1980-12-31 | Ciba Geigy Ag | |
CA1270998A (en) * | 1986-07-15 | 1990-06-26 | Akihiro Yamaguchi | Thermosetting resin composition |
DE3883134T2 (de) * | 1987-10-08 | 1994-04-14 | Mitsui Toatsu Chemicals | Aromatische Aminharze, ihr Herstellungsverfahren und diese verwendende wärmehärtende Harzmischungen. |
CH681232A5 (zh) * | 1989-12-22 | 1993-02-15 | Rieter Ag Maschf |
-
1988
- 1988-05-17 JP JP63118363A patent/JPH075737B2/ja not_active Expired - Fee Related
-
1989
- 1989-05-15 US US07/351,471 patent/US4959443A/en not_active Expired - Fee Related
- 1989-05-15 CA CA000599626A patent/CA1333947C/en not_active Expired - Fee Related
- 1989-05-17 KR KR1019890006591A patent/KR930002238B1/ko not_active IP Right Cessation
- 1989-05-17 CN CN89103316A patent/CN1037721A/zh active Pending
- 1989-05-17 EP EP89304963A patent/EP0342943B1/en not_active Expired - Lifetime
- 1989-05-17 DE DE89304963T patent/DE68908009T2/de not_active Expired - Fee Related
- 1989-05-17 AU AU34895/89A patent/AU611801B2/en not_active Ceased
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1317329C (zh) * | 2003-11-05 | 2007-05-23 | 三井化学株式会社 | 树脂组合物、使用该树脂组合物的预浸料及叠层板 |
Also Published As
Publication number | Publication date |
---|---|
JPH01289834A (ja) | 1989-11-21 |
EP0342943B1 (en) | 1993-08-04 |
EP0342943A1 (en) | 1989-11-23 |
CA1333947C (en) | 1995-01-10 |
AU3489589A (en) | 1989-11-23 |
DE68908009T2 (de) | 1994-03-10 |
KR930002238B1 (ko) | 1993-03-27 |
DE68908009D1 (de) | 1993-09-09 |
JPH075737B2 (ja) | 1995-01-25 |
AU611801B2 (en) | 1991-06-20 |
US4959443A (en) | 1990-09-25 |
KR900018275A (ko) | 1990-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1319214C (en) | Blended polyamide oligomers | |
KR910002086B1 (ko) | 폴리이미드 수지조성물 | |
KR101967890B1 (ko) | 말레이미드 수지 | |
CN1053680C (zh) | 热固性化合物、其固化产品与制备该化合物的方法 | |
CN111763323B (zh) | 聚硅氧烷改性四烯丙基化合物、热修复双马树脂组合物及制备方法 | |
CN1037721A (zh) | 热固性树脂组合物 | |
US4621134A (en) | Aromatic polythioetheramide | |
JP6550136B2 (ja) | 三官能性ベンゾオキサジン並びに硬化性樹脂組成物及び複合材料におけるその使用 | |
CN114599707A (zh) | 邻苯二甲腈树脂及其制备方法和组合物 | |
JP2759796B2 (ja) | 新規なビス(マレイミド)シロキサンおよびその製造方法 | |
CA1312875C (en) | Aromatic amine resins, their production process and thermosetting resin compositions making use of the same | |
CN111704719B (zh) | 一种热固性聚酰亚胺树脂、预聚物、制备方法与应用 | |
PT86926B (pt) | Processo para a preparacao de polimeros termoestaveis a base de maleimidas uma das quais e eventualmente um bis-maleimido-siloxano e de diamino-siloxanos | |
EP0451405B1 (en) | Thermosetting resin composition | |
CN1259530A (zh) | 植物油改性苯并恶嗪中间体及其制备方法和用途 | |
EP0266708B1 (en) | Cross-linked resins and production thereof | |
CN114195769B (zh) | 一种聚酰亚胺改性剂、组合物及其制备方法 | |
CN100540573C (zh) | 一种用间苯二炔丙基醚改性的双马来酰亚胺树脂及其制备方法 | |
JP2543970B2 (ja) | 熱硬化性樹脂組成物 | |
JPH0458808B2 (zh) | ||
CN1017055B (zh) | 生产芳香胺树脂的方法 | |
CN111662455A (zh) | 聚硅氧烷改性双马单体、热修复双马树脂组合物及制备方法 | |
JPH0559933B2 (zh) | ||
CN115368563A (zh) | 无溶剂法制备含醛亚胺键双邻苯二甲腈化合物、聚合物及其应用 | |
JPH0822950B2 (ja) | 熱硬化性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C01 | Deemed withdrawal of patent application (patent law 1993) | ||
WD01 | Invention patent application deemed withdrawn after publication |